Selectivity of Bio-oils Catalytic Hydrotreatment Assessed by Petroleomic and GC*GC/MS-FID Analysis

Abstract

We propose to assess the selectivity of hydrotreatment catalysts by two complementary analytical methods: (1) high-resolution mass spectrometry (MS), called “petroleomic” analysis, by Fourier transform ion cyclotron resonance (FT ICR, 9.4T) MS for species heavier than m/z of about 200 Da and (2) quantitative GC*GC (heart-cutting)/MS-flame ionization detector (FID) analysis of lighter species. The methodology is illustrated on methanol-soluble bio-oils produced by lignin pyrolysis and hydrotreated by iron-based catalysts. GC*GC analysis is calibrated by a combination of internal standard and prediction of response factors on the FID. Laser desorption ionization (LDI) and electro spray ionization (ESI) in negative-ion mode are combined for the petroleomic analysis. The selectivity of hydrotreatment (catalytic fixed bed, 1 atm, 400 °C) is assessed as a function of catalyst loads and iron support (silica and activated carbon). Hundreds of species are analyzed by GC*GC and petroleomic and mapped in Van Krevelen diagrams. The high selectivity of reduced iron for the hydrodeoxygenation of lignin pyrolysis vapors is demonstrated. The effect of the catalytic treatment on oxygen content and unsaturation is studied for a broad range of species: from C2 to C14 by GC analysis and from C8 to C37 by petroleomic. Many heavy lignin oligomers produced by the pyrolysis are trapped by the catalytic bed, highlighting the need of new catalytic systems to convert them into valuable fuels or chemicals.

Gas chromatography coupled to atmospheric pressure ionization mass spectrometry (GC-API-MS): Review

“…However, the combination of GC-MS and GC-FID has never developed into a routine analytical method, due to considerable technical problems with the synchronization of FID and vacuum-stage MS [89]. They are running mostly separately [88,95,96] or in heart cut mode [97]. But in some cases, the use of parallel detectors was also reported [98,99].…”

IOFI recommended practice for the use of predicted relative‐response factors for the rapid quantification of volatile flavouring compounds by GC‐FID

“…This technique, described in a number of publications, [2][3][4][5] with applications reported in the flavour, fragrance, and other domains, [6][7][8][9][10][11][12] can also be used to estimate the purity of chemically-defined flavouring substances or chromatographic standards using these predicted RRF.…”

Study of the mainstream cigarette smoke aerosols by Fourier transform ion cyclotron resonance mass spectrometry coupled to laser/desorption and electrospray ionization – Additional insights on the heteroaromatic components

“…The increase in the laser fluence generally leads to a recombination phenomenon which may be associated with the clustering phenomenon . To increase the knowledge of the composition of the cigarette smoke particle fraction, electrospray ionization (ESI) may be regarded as a complementary ionization technique as recently demonstrated for bio‐oil analysis . Indeed, the ability of ESI to efficiently ionize polar compounds, which are poorly detected by LDI, may be helpful to obtain a more complete description of such complex samples.…”